Liquid non-aqueous dispersion and process for producing the same

ABSTRACT

A liquid non-aqueous dispersion comprising a silicone oil and a copolymer dispersed therein, the copolymer comprising (A) at least one radical polymerizable macromonomer containing dimethyl polysiloxane, and (B) at least one radical copolymerizable monomer with the macromonomer (A), which comprises at least one (meth)acrylate monomer and optionally at least one vinyl monomer. This liquid non-aqueous dispersion has excellent water resistance, oil resistance and adhesive properties, and when used as a component of cosmetics, it can meet both requirements for long lasting make-up and good feeling of use of cosmetics.

This is a continuation application of U.S. application Ser. No.10/314,412 filed Dec. 9, 2002, now U.S. Pat. No. 7,247,672.

BACKGROUND OF THE INVENTION

The present invention relates to a liquid non-aqueous dispersion havinga copolymer dispersed in a silicone oil, and a process for producingsuch a dispersion.

Various types of polymers have been used as one of base materials ofcosmetics for the purpose of providing cosmetics with such functions aswater resistance, oil resistance and adhesion to the skin and makingcosmetics keep long. For example, high-molecular weight polymers such aspolyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetate, acrylicester-based resins, nitrocellulose, alkyd resins, polyamide resins,methoxyethylene/maleic anhydride copolymer and alkanolamine solution ofacrylic resins have been used as a base material of cosmetics such asmakeup cosmetics, hair cosmetics, nail cosmetics and basic cosmetics.

Cosmetics containing these polymers are indeed improved in durability,but since the coating film formed on the human bodies by application ofthe cosmetics containing these polymers becomes a continuous film inwhich the polymer chains are intertwined with each other without aspecial design, these cosmetics have the problem that they are ratherawkward to be applied by users because the cosmetics give the users suchan unpleasant feeling that the human bodies are pulled by the coatingfilm formed. Thus, it was hardly possible to increase the polymercontent in the cosmetic formulations, so that a cosmetic materialexcellent in long-keeping quality has not been obtained.

Under these circumstances, development of a polymer useful for acosmetic material that can provide cosmetics having good feeling of useand excellent long-keeping quality has been desired.

Use of silicone-acrylic resins as such a polymer has been proposed as asolution to the above problem, and many researches have been made forthe improvement of spread, removal of rough feeling and otherdisagreeable qualities of cosmetics by taking advantage of slipproperties of the silicone component.

For instance, JP-A-2-247110 tries to satisfy both requirements fordurability and good feeling of use of cosmetics by compounding asilicone-acrylic graft polymer. According to this method, however, whencosmetics blended with the polymer are applied, the coating film formedon the surface of the human body becomes a continuous film in which thepolymer chains are intertwined with each other because the polymer usedis the one which has been synthesized by a solution polymerizationtechnique. Therefore, feeling of use of these cosmetics was stillunsatisfactory, and there was also a restriction on the amount ofpolymer that can be compounded.

JP-A-8-269332 proposes to blend in cosmetics a non-aqueous resindispersion prepared by dispersing an acrylic polymer in a hydrophobicmedium such as silicone oil by using a silicone-based dispersant resin.In this case, however, as the dispersion is produced by a two-steppolymerization method using a large quantity of a high-molecular weightsilicone-based dispersant resin which has been previously produced bypolymerization, the product assumes a state of solution in which thesilicone moiety of the silicone-based dispersant resin is dissolved in ahydrophobic medium, and the obtained dispersion does not become aperfect dispersion system and is highly viscous. Further, since thecoating film formed after application of cosmetics is a continuous filmin which silicone segments of the silicone moiety of the silicone-baseddispersant resin are similarly intertwined with each other, feeling ofuse of cosmetics is not improved.

Thus, for a material of cosmetics, it is desirable to blend such apolymer dispersion that polymer chains existed on the surfaces of thepolymer particles are not intertwined with each other and polymerparticles stand in a two dimensional array on the surface of the humanbody as a film when applying the cosmetics, but there has yet beenavailable no polymer dispersion that can meet the requirement forproviding cosmetics with good feeling of use.

Accordingly, an object of the present invention is to provide a polymerdispersion capable of offering cosmetics which have the above-mentionedproperties, good water resistance, oil resistance and adhesive qualitiesto help make-up last longer, can be applied with no resistance, and givegood sense of use without causing a disagreeable feeling that thesurface of the human body after application of cosmetics is pulled bythe coating film formed.

It is also an object of the invention to provide the polymer dispersionin the form of a liquid non-aqueous preparation.

SUMMARY OF THE INVENTION

The present inventors have found that each of the following featureshave contributed to the deterioration of the feeling of use of cosmeticscontaining a high-molecular weight polymer:

-   1) In the solution type polymers, the polymers form such a state    that they are dissolved in a solution, while the polymer chains are    intertwined with each other, so that the coating film formed after    application of cosmetics is a continuous film in which the polymer    chains still remain intertwined with each other;-   2) In the emulsion type polymers, although the polymer particles are    dispersed in a solution, fusion of the polymer particles takes place    when a coating film is formed on application of cosmetics, so that    the formed coating film assumes a state where the polymer chains are    intertwined with each other.

The present inventors have also found that in order to solve the aboveproblems causes, it is essential that:

-   1) The polymer particles remain dispersed in a solution; and-   2) Even after a coating film has been formed by application of    cosmetics, the polymer chains on the particle surfaces are not    intertwined between the dispersed polymer particles, and the polymer    particles aggregate while physically maintaining their shape.

Various methods, such as ICI method (JP-B-40-23350), Cook Paint method(JP-B-47-21581) and Ford method (JP-B-47-8537), have been known forproducing a non-aqueous dispersed polymer for obtaining a desireddispersion condition.

In the above methods, there are first synthesized the components solublein hydrocarbons in a hydrocarbon-based hydrophobic solvent, and then thecomponents insoluble in hydrocarbons are graft polymerized to attainstabilization of dispersion. However, as a result of investigations bythe present inventors, it has been found that:

-   1) These methods are complicated, and it is difficult to prepare a    high-concentration solution by these methods;-   2) There is a limitation on composition for obtaining a stabilized    dispersion.-   3) In these methods, stabilized dispersion is acquired by arranging    the soft components soluble in hydrocarbons on the dispersed    particle surfaces, so that the formed coating film is a continuous    film in which the polymer chains are intertwined with each other.

Further studies on these problems by the present inventors have led tothe attainment of the present invention.

Thus, the present invention provides a liquid non-aqueous polymerdispersion comprising a silicone oil and a copolymer dispersed therein,said copolymer comprising (A) 1 to 20% by weight of at least one radicalpolymerizable macromonometer containing dimethyl polysiloxane, which isrepresented by the following formula (1):

(wherein X represents a radical polymerizable group, n is an integer of1 to 10, and m is an integer of 3 to 300), and (B) 99 to 80% by weightof at least one radical copolymerizable monomer with said component (A),which comprises at least one (meth)acrylate monomer and optionally atleast one vinyl monomer.

In the polymer dispersion of the present invention, dimethylpolysiloxane groups are dispersed in a silicone oil in such a state thatthey are arranged on the copolymer particle surfaces, so that when thisdispersion is blended in a cosmetic preparation and the resultingcosmetic is applied on the skin, a coating film is formed in which thedispersed copolymer particles aggregate to each other. Thus,incorporation of said dispersion in cosmetics makes it possible to forma coating film having excellent water and oil resistance, easy to applyand free of any disagreeable feeling on application.

DETAILED DESCRIPTION OF THE INVENTION

As mentioned above, the liquid non-aqueous dispersion of the presentinvention is a dispersion having a copolymer dispersed in a siliconeoil. The copolymer used in the present invention is one obtained bycopolymerizing (A) at least one radical polymerizable macromonomercontaining dimethyl polysiloxane and (B) at least one radicalcopolymerizable monomer with said macromonomer.

The silicone oils usable in the present invention include dialkylpolysiloxanes such as dimethyl polysiloxane, diethyl polysiloxane anddibutyl polysiloxane; alkylphenyl polysiloxanes such as methylphenylpolysiloxane and ethylphenyl polysiloxane; cyclic dialkyl polysiloxanessuch as cyclic dimethyl polysiloxane, cyclic diethyl polysiloxane andcyclic dibutyl polysiloxane; and cyclic alkylphenyl polysiloxanes suchas cyclic methyphenyl polysiloxane, cyclic ethylphenyl polysiloxane andcyclic butylphenyl polysiloxane. Modified polysiloxanes such asamino-modified polysiloxanes, polyether-modified polysiloxanes andalkyl-modified polysiloxanes may be also used. These silicone oils maybe used either alone or as a combination of two or more of themaccording to the purpose of the cosmetic.

The radical polymerizable macromonomer (A) containing dimethylpolysiloxane is represented by the following formula (1):

(wherein X represents a radical polymerizable group, n is an integer of1 to 10, and m is an integer of 3 to 200).

Examples of the radical polymerizable groups represented by X in theabove formula are acryloxy group, methacryloxy group, styryl group,allyl group, vinylbenzene group, vinyl ether group, acrylamide group,vinylalkylsilyl group, and vinyl ketone group.

Examples of the macromonomer (A) are dimethylpolysiloxypropylacrylicester, dimethylpolysiloxypropylmethacrylic ester,dimethylpolysiloxypropylbenzyl ether,dimethylpolysiloxypropylacrylamide, and dimethylpolysiloxypropionicvinylbenzilate. Among them, dimethylpolysiloxypropylacrylic ester anddimethylpolysiloxypropylmethacrylic ester are particularly preferred.

The number-average molecular weight of macromonomer (A) is 1,000 to100,000, preferably 2,000 to 50,000 in terms of polystyrene valuemeasured by GPC. When it is less than 1,000, dispersion stability isunsatisfactory, and when it exceeds 100,000, the produced dispersionbecomes too high in viscosity. These macromonomers can be used eitheralone or as a combination of two or more.

Macromonomer (A) is a component dissolved in a silicone oil, and itsamount is 1 to 20% by weight, preferably 2 to 15% by weight of the totalamount of monomers. When its amount exceeds 20% by weight, the obtainedcopolymer may be dissolved in silicone oil, making cosmetics lessconvenient to apply. Cosmetics may also have stickiness derived from themacromonomer. On the other hand, when the amount of macromonomer (A) isless than 1% by weight, no stabilized dispersion can be obtained.

Radical copolymerizable monomer (B) with the macromonomer (A) containsat least one (meth)acrylate monomer as an essential component and mayoptionally contain at least one vinyl monomer copolymerizable with the(meth)acrylate monomer.

The (meth)acrylate monomers are different from the macromonomers (A) inpolarity, so that in the present invention it is possible to useordinary (meth)acrylates without restrictions. Therefore, in thepolymerization process in a silicone oil having strong hydrophobicproperties, the (meth)acrylate monomers having relatively high polarityas compared with the silicone oil, namely, hydrophilic monomers areburied in the core part of the polymer particle in the non-aqueousdispersion. Such (meth)acrylate monomers may be used either alone or asa combination of two or more. Examples of these (meth)acrylate monomersinclude alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl(meth)acrylate, N-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,stearyl (meth)acrylate, benzyl (meth)acrylate and cyclohexyl(meth)acrylate; hydroxyl group-containing (meth)acrylates, for example,hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and2-hydroxypropyl (meth)acrylate; carboxyl group-containing monomers suchas acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaricacid, maleic acid and their half esters; phosphate group-containing(meth)acrylates such as LIGHT ESTER PA and LIGHT ESTER PM (both beingproduced by Kyoei Chemical Co., Ltd.): basic (meth)acrylates such asN,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl(meth)acrylate; epoxy group-containing (meth)acrylates such as glycidyl(meth)acrylate; N-alkoxy-substituted amides such as N-methoxymethylol(meth)acrylamide and N-butoxymethylol (meth)acrylamide; andcarbonyl-containing monomers such as diacetone acrylamide andacetoacetoxyethyl methacrylate.

Examples of the vinyl monomer copolymerizable with the (meth)acrylatemonomer, which is an optional component, include aromatic vinyls such asstyrene, acephamethylstyrene and vinyltoluene; unsaturated nitriles suchas (meth)acrylonitrile; and vinyl esters such as vinyl acetate and vinylpropionate. Further, polyfunctional vinyl monomers such asdivinylbenzene, trimethylolpropane tri(meth)acrylate, ethylene glycoldi(meth)acrylate, etc., may be used as an optional component togetherwith a (meth)acrylate monomer. These monomers may be used either aloneor as a combination of two or more of them.

The amount of monomer (B) is 99 to 80% by weight, preferably 98 to 85%by weight of the total amount of monomers.

Glass transition temperature (Tg) of the copolymer consisting ofmacromonomer (A) and monomer (B) is −30 to 80° C., preferably 10 to 50°C. If Tg is below −30° C., the coating film is not provided withsufficient strength, and if Tg is above 80° C., the film formingproperties are poor and film adhesion is unsatisfactory.

The liquid non-aqueous dispersion according to the present invention canbe obtained by subjecting macromonomer (A) and monomer (B) to one-stepradical polymerization in a silicone oil such as mentioned above in thepresence of a radical polymerization initiator without using anydispersion stabilizer.

As the radical polymerization initiator, any of those commonly employedfor ordinary radical polymerization can be used, the examples thereofbeing azo compounds such as 2,2-azobisisobutyronitrile,2,2-azobis(2,4-dimethylvaleronitrile),2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile) and dimethyl2,2-azobisisobutyrate; and organic peroxides such as lauroyl peroxide,t-butyl peroxide, dicumyl peroxide, t-butylperoxy-2-ethylhexanoate andbenzoyl peroxide.

The amount of polymerization initiator is preferably 0.01 to 5% byweight, more preferably 0.1 to 2% by weight of the total amount ofmonomers.

A chain transfer agent such as mercaptoacetic acid, mercaptopropionicacid, 2-propanethiol, 1-butanethiol, 2-mercaptoethanol, ethylmercaptoacetate, thiophenol, 2-naphthalenethiol, dodecylmercaptan, etc.,may be used in polymerization for the adjustment of molecular weight.

The polymerization reaction is usually carried out in a silicone oil attemperatures ranging from 30 to 180° C., preferably 80 to 150° C. Thereaction can be completed in about 5 to 10 hours by adding or addingdropwise continuously macromonomer (A), monomer (B), polymerizationinitiator and other necessary substances to the silicone oil under theabove conditions.

It is considered that when macromonomer (A) and monomer (B) aresubjected to radical copolymerization in a silicone oil, withmacromonomer (A) being dissolved in the silicone oil in appearance,monomer (B) is increased in molecular weight and insolubilized in thesilicone oil as the polymerization reaction proceeds, thereby causing aphase transformation with dimethyl polysiloxane coming on the outsideand the acrylic component staying on the inside in a rounded form. Thus,such a dispersion structure that the copolymer of macromonomer (A) andmonomer (B) is dispersed in the silicone oil can be formed.

Therefore, dispersion stability and particle size are decided bychanging the copolymer composition of macromonomer (A) and monomer (B),and it is possible to control the particle size and molecular weight ofthe copolymer dispersed in the silicone oil by adjusting the kind ofmonomer (B), polymerization reaction temperature, the kind and amount ofpolymerization initiator (catalyst) and the way of addition of themonomers.

The weight-average molecular weight of the copolymer dispersed insilicone oil is preferably within the range of 5,000 to 500,000,particularly 10,000 to 100,000, in terms of polystyrene value measuredby GPC. If the molecular weight is less than 5,000, the product becomessticky, and if the molecular weight exceeds 500,000, the product fallsshort of film forming properties and lowers in adhesion.

The particle size of the copolymer dispersed in silicone oil ispreferably from 0.05 to 2.0 μm, particularly 0.1 to 0.8 μm for obtaininga coating film having desired transparency. When the particle sizeexceeds 2.0 μm, the dispersed particles of the copolymer become unstableand also transparency of the coating film deteriorates.

The dispersed particles of the copolymer in silicone oil, obtained inthe manner described above, have such a structure thatpolydimethylsiloxane is existed on their surfaces, so that in additionto excellent water resistance, oil resistance and adhesive propertiesattained by the copolymer itself, because of low viscosity, the productcan spread well even in the course of drying, is easy to apply and givesa pleasant feeling on application. Further, since the formed coatingfilm is free of intertwining of molecular chains, the skin is notbothered by an uncomfortable feeling due to stretch. Thus, the liquidnon-aqueous dispersion of the present invention has the advantages whichcannot be found in the conventional liquid non-aqueous dispersions.

As explained above, by incorporating the liquid non-aqueous dispersionof the present invention in a cosmetic base, it is possible to satisfyboth requirements for long lasting make-up and good feeling of use ofcosmetics which could not be achieved by use of the conventionalpolymers and polymer dispersions. The liquid non-aqueous dispersion ofthe present invention, therefore, can be used widely as a componentmaterial for a variety of cosmetics, for example, make-up cosmetics suchas foundation, powder, cheek rouge, eye shadow and mascara, haircosmetics such as hair color, hair spray, hair foam and hairdye, nailcosmetics such as nail cream and nail enamel, lip cosmetics such asrouge and lip cream, eyeliner cosmetics, basic cosmetics such as cream,milky lotion (emulsion) and lotion, and cleansing cosmetics such asshampoo and rinse.

DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention will be described in further detail by showing thefollowing examples, but, the examples are merely intended to beillustrative and not to be construed as limiting the scope of theinvention.

Preparation of Silicone Oil-Dispersed Polymer Solution Example 1

400 g of a commercial silicone oil KF-995 (decamethylcyclopentasiloxaneproduced by Shin-Etsu Chemical Industries Co., Ltd.) was added to areactor equipped with a thermometer, a reflux condenser, a stirrer and adropping funnel, and after replacing the reactor atmosphere withnitrogen gas, the silicone oil was heated and maintained at 120° C. Tothis, a mixture of 336 g of methyl methacrylate (MMA), 224 parts of2-ethylhexyl acrylate (2EHA), 40 g of a commercial silicone macromonomerFM-0721 (polydimethylsiloxypropylacrylic ester; mono-terminal SAILAPLANEproduced by Chisso Corp., having the following formula:

and an average molecular weight of 5,000) and 9 g oftert-butylperoxy-2-ethyl hexanoate (PBO) as polymerization initiator wasadded dropwise over a period of 180 minutes. After the completion ofthis dropwise addition, the mixture was maintained at the sametemperature for 3 hours and then cooled to obtain a milky whitedispersed polymer solution with a solid content of 60.2% and a viscosityof 3.6 Ps.

The weight-average molecular weight of the thus obtained dispersedpolymer, as determined by GPC, was 31,000. The average particle size ofthe dispersion, as determined by using a laser doppler/frequencyanalysis type particle size analyzer (UPA150 mfd. by Nikkisoh Ltd.), was0.27 μm.

Example 2

According to the procedure of Example 1, 400 g of KF-995 was added tothe reactor and heated and maintained at 120° C., to which a mixture of270 g of methyl methacrylate, 250 g of butyl acrylate (BA), 40 g of2-hydroxyethyl methacrylate (2HEMA), 40 g of FM-0725 (having the samestructure as FM-0721 with an average molecular weight of 10,000,produced by Chisso Corp.) and 9 g of tert-butylperoxy-2-ethyl hexanoatewas added dropwise over a period of 180 minutes. The mixture wasmaintained at the same temperature for 3 hours and then cooled to obtaina milky white dispersed polymer solution with a solid content of 60.1%and a viscosity of 5.3 Ps.

The weight-average molecular weight of the resulting dispersed polymerwas 28,000, and its average particle size was 0.28 μm.

Example 3

According to the procedure of Example 1, 400 g of KF-994(decamethylcyclopentanesiloxane produced by Shin-Etsu ChemicalIndustries Co., Ltd.) was added to the reactor instead of KF-995, towhich a mixture of 50 g of methyl methacrylate, 460 g of butylmethacrylate (BMA), 30 g of butyl acrylate, 60 g of FM-0721 and 4 g oftert-butylperoxy-2-ethyl hexanoate was added dropwise at 110° C. over aperiod of 180 minutes. The mixture was maintained at the sametemperature for another 180 minutes and then cooled to obtain a milkywhite dispersed polymer solution with a solid content of 60.2% and aviscosity of 4.3 Ps.

The weight-average molecular weight of the dispersed polymer was 52,000and its average particle size was 0.30 μm.

Comparative Example 1

400 g of toluene (TOL) was added to a reactor equipped with athermometer, a reflux condenser, a stirrer and a dropping funnel, andafter replacing the reactor atmosphere with nitrogen gas, TOL was heatedand maintained at 110° C. To this, a mixture of 336 g of methylmethacrylatel, 224 parts of 2-ethylhexyl acrylate, 40 g of a commercialsilicone macromonomer FM-0721 and 9 g of tert-butylperoxy-2-ethylhexanoate as polymerization initiator was added dropwise over a periodof 180 minutes. After completion of this dropwise addition, the mixturewas maintained at the same temperature for 3 hours and then cooled toobtain a transparent polymer solution with a solid content of 60.3% anda viscosity of 52.7 Ps.

The weight-average molecular weight of the obtained polymer was 29,000.

Comparative Example 2

According to the procedure of Comparative Example 1, 500 g of toluenewas added to the reactor and heated and maintained at 110° C., to whicha mixture of 220 g of methyl methacrylate, 90 parts of 2-ethylhexylacrylate, 150 g of FM-0721 and 9 g of tert-butylperoxy-2-ethyl hexanoateas polymerization initiator was added dropwise over a period of 180minutes. After completion of the dropwise addition, the mixture wasmaintained at the same temperature for 3 hours and then cooled to obtaina translucent polymer solution with a solid content of 50.2% and aviscosity of 23.4 Ps. The weight-average molecular weight of theresulting polymer was 32,000.

100 g of the resulting polymer was poured into 1,000 g of methanol tolet the polymer precipitate. The precipitate was separated and dried toobtain the solid polymer.

Comparative Example 3

According to the procedure of Example 1, 500 g of KF-995 was added tothe reactor and heated and maintained at 110° C., to which a mixture of220 g of methyl methacrylate, 90 g of butyl methacrylate, 150 g ofFM-0721 and 9 g of tert-butylperoxy-2-ethyl hexanoate was added dropwiseover a period of 180 minutes. After this, the mixture was maintained atthe same temperature for 3 hours and then cooled to obtain a milky whitedispersed polymer solution with a solid content of 50.2% and a viscosityof 2.5 Ps.

The weight-average molecular weight of the dispersed polymer was 32,000and its average particle size was 0.25 μm.

Comparative Example 4

According to the procedure of Example 1, 400 g of KF-995 was added tothe reactor and heated and maintained at 120° C., to which a mixture of480 g of methyl methacrylate, 60 g of styrene (ST), 20 g of butylacrylate, 40 g of FM-0721 and 9 g of tert-butylperoxy-2-ethyl hexanoatewas added dropwise over a period of 180 minutes. The mixture wasmaintained at the same temperature for another 3 hours and then cooledto obtain a milky white dispersed polymer solution with a solid contentof 60.2% and a viscosity of 2.8 Ps. The weight-average molecular weightof the dispersed polymer was 29,000 and its average particle size was0.26 μm.

Properties of the polymers obtained in Examples 1 to 3 and ComparativeExamples 1 to 4 are shown in Tables 1 and 2.

TABLE 1 Polymerization conditions of the dispersed polymer in siliconeoil Example Comp. Example 1 2 3 1 2 3 4 Solvent (g) KF-995 400 400 500400 KF-994 400 TOL 400 500 Silicone macromonomer (g) FM-0721 40 60 40150 150 40 FM-0725 40 Monomers (g) ST 60 MMA 336 270 50 336 220 220 480BMA 460 BA 250 30 20 2EHA 224 224 90 90 2HEMA 40 Catalyst (g) PBO 9 8 49 9 9 9 Reaction temperature (° C.) 120 120 110 110 110 110 120

TABLE 2 Properties of the dispersed polymer in silicone oil ExampleComp. Example 1 2 3 1 2 3 4 Solid content (wt. %) 60.2 60.1 60.2 60.350.2 50.2 60.2 Viscosity (ps) 3.6 5.3 4.3 52.7 23.4 2.5 2.8 Averageparticle size (μm) 0.27 0.29 0.30 — — 0.25 0.26 Weight-average molecularweight 31000 25000 52000 29000 32000 32000 29000 Tg of acryl moiety (°C.) 8.1 8.7 19.7 8.1 27.3 27.3 94.5 Content of silicone macromonomer 7.110 7.1 7.1 30 30 7.1 (wt. %)

Performance of the obtained polymers was examined by the following testprocedures and evaluated according to the evaluation criteria as shownbelow. Results are shown in Table 3.

Test Procedures

(1) Transparency

The dispersion to be tested was applied on a transparent glass plate toform a film at 20° C. and 65% RH so that the dry film thickness is 20μm, and the degree of cloudiness of the resulting film was visuallydetermined.

(2) Water Resistance

The dispersed resin solution was applied on a clean fluorine film toform a coating film so that the dry film thickness is 20 μm. Afterdrying, the coating film was stripped off and immersed in tap water for3 days, and then the change of status of the coating film was visuallyobserved.

(3) Oil Resistance

A coating film was formed in the same way as in the method of the above(2) and immersed in indodecane for 24 hours, and the change of status ofthe coating film was visually observed.

(4) Adhesion to the Skin

A few drops of the dispersion were applied on the back of a hand, andafter drying, the formed film was rubbed with fingers. Adhesion to theskin was judged by the difficulty in removing the film from the skin.

(5) Applicability

Applicability of the dispersion was determined by the “hitch” inspreading the dispersion on the back of a hand with fingers until it wasdried to form a film.

(6) Conformability to Skin

This was determined by the sense of stretch on the skin given by thefilm formed according to the above (5) after it was dried.

TABLE 3 Evaluation results Example Comp. Example 1 2 3 1 2 3 4 Coatingfilm quality Transparency ◯ ◯ ◯ ◯ ◯ ◯ — Water resistance ◯ ◯ ◯ ◯ ◯ ◯ —Oil resistance ◯ ◯ ◯ ◯ ◯ ◯ — Adhesion ◯ ◯ ◯ ◯ ◯ ◯ X Use characteristicsApplicability ⊚ ⊚ ⊚ X X Δ ⊚ Conformability to skin ⊚ ⊚ ⊚ X X Δ —Criterion for evaluation ⊚: Very good; ◯: Good; Δ: Rather bad; X : Bad

Preparation of Cosmetics Examples of Compounding in Liquid FoundationExample 4

The following components (1) to (10) were mixed and dispersed uniformlyby a sand grinder to obtain a liquid foundation:

(1) Dispersed polymer in silicone oil (Example 1) 45.0 g  (2)Dimethylpolysiloxane 5.3 g (3) Isoparaffin (Isopar K*) 9.0 g (4)Titanium oxide 19.3 g  (5) Red iron oxide 1.2 g (6) Yellow iron oxide2.7 g (7) Black iron oxide 0.9 g (8) Mica 12.0 g  (9) Talc 4.5 g (10)Perfume 0.1 g *Produced by Exxon Chemical Co., Ltd.

Comparative Example 5

The following components (1) to (5) were mixed and dissolved underheating, then the remaining components (6) to (11) were added, and thesecomponents were dispersed uniformly by a roll mill to obtain a liquidfoundation:

(1) Solid polymer obtained in Comparative Example 2 15.0 g  (2)Dimethylpolysiloxane 9.0 g (3) Decamethylcyclopentasiloxane 6.0 g (4)Isoparaffin (Isopar K) 39.8 g  (5) Titanium oxide 12.9 g  (6) Red ironoxide 0.8 g (7) Yellow iron oxide 1.8 g (8) Black iron oxide 0.6 g (9)Mica 8.0 g (10) Talc 3.0 g (11) Perfume 0.1 g

Results of evaluation of the liquid foundations obtained in Example 4and Comparative Example 5 are shown in Table 4.

TABLE 4 Evaluation results Example Comp. Example 4 5 Spread ⊚ ΔLightweight feeling ◯ ◯ Absence of uncomfortable feeling ⊚ Δ Lastingmake-up ◯ ◯ Criterion for evaluation ⊚: Very good; ◯: good; Δ: Ratherbad; X: Bad

1. A liquid non-aqueous dispersion comprising a silicone oil and aparticulate copolymer dispersed therein without the presence of adispersion stabilizer, wherein a viscosity of the dispersion is 3.6 to5.3 Ps and a particle size of the particulate copolymer is 0.05 to 2.0μm, wherein said copolymer is obtained by one-step copolymerizing (A) 1to 20% by weight of at least one radical polymerizable macromonomercontaining dimethyl polysiloxane, the macromonomer (A) being representedby the formula (1):

(wherein X represents a radical polymerizable group, n is an integer of1 to 10, and m is an integer of 3 to 300), and (B) 99 to 80% by weightof at least one radical copolymerizable monomer with said macromonomer(A), the monomer (B) comprising at least one (meth)acrylate monomer andoptionally at least one vinyl monomer, in a silicone oil without usingany dispersion stabilizer.
 2. A liquid non-aqueous dispersion accordingto claim 1, wherein the radical polymerizable macromonomer is at leastone substance selected from the group consisting ofdimethylpolysiloxypropylacrylic ester,dimethylpolysiloxypropylmethacrylic ester,dimethylpolysiloxypropylvinylbenzyl ether,dimethylpolysiloxypropylacrylamide and dimethylpolysiloxypropionicvinylbenzylate.
 3. A liquid non-aqueous dispersion according to claim 2,wherein the radical polymerizable macromonomer isdimethylpolysiloxypropylacrylic ester ordimethylpolysiloxypropylmethacrylic ester.
 4. A liquid non-aqueousdispersion according to claim 1, wherein the (meth)acrylate monomer isat least one selected from the group consisting of methyl methacrylate,butyl methacrylate, butyl acrylate, 2-ethylhexyl methacrylate and2-hydroxyethyl methacrylate.
 5. A liquid non-aqueous dispersionaccording to claim 1, wherein the number-average molecular weight of theradical polymerizable macromonomer is 1,000 to 100,000.
 6. A liquidnon-aqueous dispersion according to claim 1, wherein the weight-averagemolecular weight of the copolymer is 5,000 to 500,000.
 7. A liquidnon-aqueous dispersion according to claim 1, wherein the averageparticle size of the copolymer dispersed in silicone oil is 0.27 to 0.30μm.
 8. A cosmetic composition comprising the liquid non-aqueousdispersion according to claim
 1. 9. A liquid non-aqueous dispersioncomprising silicone oil and a particulate copolymer dispersed thereinwithout the presence of a dispersion stabilizer, wherein the dispersedparticles have such a structure that polydimethylsiloxane exists ontheir surfaces, in a particle size of 0.05 to 2.0 μm, wherein thecopolymer is obtained by one-step copolymerizing (A) 1 to 20% by weightof at least one radical polymerizable macromonomer containing dimethylpolysiloxane, the macromonomer (A) being represented by the formula (1):

(wherein X represents a radical polymerizable group, n is an integer of1 to 10, and m is an integer of 3 to 300), and (B) 99 to 80% by weightof at least one radical copolymerizable monomer with said macromonomer(A), the monomer (B) comprising at least one (meth)acrylate monomer andoptionally at least one vinyl monomer, in a silicone oil without usingany dispersion stabilizer.